Selective Enzymatic Oxidation of Silanes to Silanols

Compared to the biological world's rich chemistry for functionalizing carbon, enzymatic transformations of the heavier homologue silicon are rare. We report that a wild‐type cytochrome P450 monooxygenase (P450_BM3 from Bacillus megaterium, CYP102A1) has promiscuous activity for oxidation of hydrosilanes to give silanols. Directed evolution was applied to enhance this non‐native activity and create a highly efficient catalyst for selective silane oxidation under mild conditions with oxygen as the terminal oxidant. The evolved enzyme leaves C?H bonds present in the silane substrates untouched, and this biotransformation does not lead to disiloxane formation, a common problem in silanol syntheses. Computational studies reveal that catalysis proceeds through hydrogen atom abstraction followed by radical rebound, as observed in the native C?H hydroxylation mechanism of the P450 enzyme. This enzymatic silane oxidation extends nature's impressive catalytic repertoire.     

Studies on the Reactivity of 4-Acetoxy-3-acylamino-2-azetidinones: Stereospecific trans Carbon-Carbon Bond Formation

The recent publication of Reuschling and co-workers2 on the synthesis of a carbapenem utilizing, as the key step in the sequence, the stereospecific C-C coupling of 3-substituted-acetoxy-2-azetidinones with cuprates, prompts us to report our related work in this area.     

Stability of Partially Implicit Langevin Schemes and Their MCMC Variants

A broad class of implicit or partially implicit time discretizations for the Langevin diffusion are considered and used as proposals for the Metropolis–Hastings algorithm. Ergodic properties of our proposed schemes are studied. We show that introducing implicitness in the discretization leads to a process that often inherits the convergence rate of the continuous time process. These contrast with the behavior of the naive or Euler–Maruyama discretization, which can behave badly even in simple cases. We also show that our proposed chains, when used as proposals for the Metropolis–Hastings algorithm, preserve geometric ergodicity of their implicit Langevin schemes and thus behave better than the local linearization of the Langevin diffusion. We illustrate the behavior of our proposed schemes with examples. Our results are described in detail in one dimension only, although extensions to higher dimensions are also described and illustrated.     

On the photoelectron spectrum of sulphur trioxide

He(I), He(II) and variable temperature Ne(I) photoelectron spectra of sulphur trioxide are reported. All six of the expected ionic states have been detected and assigned; the assignment differs from a previous one. Ab initio calculations in a medium basis set have been carried out and spectral intensities have been calculated; agreement between the calculations and the spectra is good. The calculations show a substantial S(3d) character in the S-O bond, and the spectra are consistent with this.     

Design of electromagnetic cloaks and concentrators using form-invariant coordinate transformations of Maxwell’s equations

The technique of applying form-invariant, spatial coordinate transformations of Maxwell’s equations can facilitate the design of structures with unique electromagnetic or optical functionality. Here, we illustrate the transformation-optical approach in the designs of a square electromagnetic cloak and an omni-directional electromagnetic field concentrator. The transformation equations are described and the functionality of the devices is numerically confirmed by two-dimensional finite element simulations. The two devices presented demonstrate that the transformation optic approach leads to the specification of complex, anisotropic and inhomogeneous materials with well directed and distinct electromagnetic behavior.     

Solution conformational preferences of glutaric, 3‐hydroxyglutaric, 3‐methylglutaric acid,and their mono‐ and dianions

Conformational preferences of glutaric, 3‐hydroxyglutaric and 3‐methylglutaric acid, and their mono‐ and dianions have been investigated with the aid of NMR spectroscopy. In contrast to succinic acid, glutaric acid displays essentially statistical conformational equilibria in polar and non‐polar solutions of high and low hydrogen‐bonding ability with no clear evidence for intramolecular hydrogen‐bonding interactions. The acid ionization constant ratios, K ₁/K₂, in D₂O and DMSO of glutaric, 3‐hydroxyglutaric, and 3‐methylglutaric acids also indicate that intramolecular interactions are much less important than, or indeed insignificant, for shorter‐chain acids. FTIR studies on 3‐methylglutaric acid indicate some preference for either association with solvent or dimerization, depending on the solvent, rather than intramolecular hydrogen bonding. Copyright © 2008 John Wiley & Sons, Ltd.     

On-line identification of diastereomeric dibenzo[a,l]pyrene diol epoxide-derived deoxyadenosine adducts by capillary electrophoresis-fluorescence line-narrowing and non-line narrowing spectroscopy.

A capillary electrophoretic method for the separation and on-line identification of closely related analytes using low-temperature fluorescence spectroscopy is reported for the eight diastereomeric deoxyadenosine (dA) adducts derived from dibenzo[a,l]pyrene diol epoxide (DB[a,l]PDE). Electrophoretic separation of stereoisomers was accomplished by application of a mixed surfactant buffer [dioctyl sulfosuccinate (DOSS) and Brij-S], which was below the critical micelle concentration (CMC) due to the high concentration (approximately 25%) of organic solvent. Addition of multiple surfactant additives to the separation buffer provided electrophoretic resolution, which was unattainable under single surfactant conditions. It is shown that the CE-separated analyte zones could be identified on-line via low-temperature (4.2 K) fluorescence non-line narrowing and fluorescence line-narrowing (FLN) spectroscopy. In addition, it was determined that in CE buffer trans-syn-,cis-syn- and cis-anti-DB[a,l]PDE-14-N6dA diastereomeric adducts exist mostly with the -dA and DB[a,l]P moiety in an "open"-type conformation while the trans-anti-DB[a,l]PDE-14-N6dA adducts exist in two different conformations whose relative distribution depends on matrix composition. The above conformations have also been revealed by selective laser excitation. Thus, the low-temperature methodology not only provides fingerprint structure via vibrationally resolved 4.2 K fluorescence spectra for adduct identification, but also provides conformational information on the spatial relationship of the carcinogen and dA moiety. These results, taken together with those for DB[a,l]P-DNA adducts formed in standard glasses and mouse epidermis exposed to DB[a,l]P, support our earlier findings that DB[a,l]P-derived adducts exist in different conformations [Jankowiak et al., Chem. Res. Toxicol. 11 (1998) 674]. Therefore, the combination of the separation power of CE and spectral selectivity of low-temperature fluorescence spectroscopy at NLN and FLN conditions provides a powerful methodology which should prove useful for identification of closely related DNA adducts formed at low levels in biological systems.